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The Gaseous Stateof Matter
Preparation for College ChemistryColumbia UniversityDepartment of Chemistry
Chapter Outline
KMT
Gas Laws
Ideal Gas Equation
Gas Stoichiometry
Air Pollution
Preliminary Observations
Molar mass of water: 18g /mole
6.02x1023 molecules weigh 18g
Density of water: 1g/cc
18 g liquid water occupies 18mL
18 g gaseous water occupies 22,400mL
Kinetic Molecular Theory of Gases
KE =1
2m c =
2p = m c
p
2m
2
v=+10cm/s
c=10cm/s
Wall
-x +x
{v=-10cm/sc=10cm/s
12
mc2 = 32
kT
Kinetic Molecular Theory of Gases
0 600 1000 1400 1800200
0.4
0.6
0.8
1.0
1.2
1.4
Molecular Speed
# M
olec
ule
s
O2 at 1000°C
O2 at 25°C
Distribution of Molecular Speeds
RategasARategasB
=dBdA
=MB
MA
Graham’s Law of Effusion
At the same T and P, the rates of Effusion of two gases are inversely proportional to their densities or molar masses.
VacuumGas
Naturally occurring Uranium : U-235 / U238 = 1 / 140
2nd step: Effusion through thousands of membranes (cascades)
1st step: U + 6 F 235 UF6 238 UF6 (g)
R235−UF6
R238−UF6
=m238−UF6
m235−UF6
=352349
=1.0043
3rd step: 235 UF6
235U Fully enriched weapons-grade Uranium
State Variables
V = volume (liters, cm3, m3)
T = temperature (in K)
P = pressure (atmospheres, mmHg, kPa)
101.325 mbar
29.9 in. Hg
14.7 lb/in2 (PSI)
76 cmHg
760 mmHg760 torr
1 atm
Torricelli’s barometer
At sea level
Atmospheric Pressure
150 kmHg height
air
0 1 3 5 7
Pressure (atm)
9
1
2
3
4
5
6
Vol
um
e (L
)
0
7
Boyle’s Law
P x V = k
At Constant TFor an Ideal Gas
P1 x V1 = P2 x V2
P1
V2
P2
V1
=
1
2
3
4
5
6
Vol
um
e (L
)
0
7
-300
T (°C)
-100 100 300 500
Charles’ Law At Constant P for an Ideal Gas
V = kT
V1
T1
V2
T2
=V T
-273°C
Absolute zero
0
1
2
3
4
5
6
Pre
ssu
re (
atm
)
7
-300
T (°C)
-100 100 300 500
P = kT
P1
T1
P2
T2
=
Gay-Lussac’s Law
At Constant V for an Ideal Gas P T
Combined Gas Laws
V1
T1
V2
T2
=
P2 V2
T2
=P1 V1
T1
Charles’ Boyle’s
V1 P1 T2
P2 T1
=V2
P1 V1 = P2 V2
STP Conditions
Standard Temperature: 273.15 K= 0.00°C
Standard Pressure: 1 atm
Reference Points for T and P for comparison
Dalton’s Law of Partial Pressures
Ptot = P1 + P2 + P3 + ...
where P1 is the partial pressure of gas 1, etc...
Pgas = Ptotal – PH2O
where PH2O is the vapor pressure of water at the specified
temperature. Most often used in collection of insoluble gases
over water. In open systems, Ptotal = Patm
Pn = Xn Ptotal
Xn =nn
n1 + n2 + n3 + ...
Molar fraction of gasn
Gay-Lussac’s Law of combining volumes
Avogadro’s Law
1809
1811
“When measured at the same T and P, the ratios of the V of reacting gases are small whole numbers”
“Equal volumes of different gases at the same T and P containthe same number of molecules”
Vn
=constant
Consequences of Avogadro’s Law
1. Explanation of Gay-Lussac’s combining volumes law. Diatomic nature of elemental gases.
2. Method for determining molar masses of gases. The molar Volume.
3. Firm foundation of KMT: gases consists of microscopic particles
Density of Gases
dV
=m
But V = f (P, T) dgasT ,P
Gas M(g/mol) d(g/L)
STPGas M(g/mol)
STPd(g/L)
H2
CH4
NH3
C2 H2
HCNCO
N2
air
H2S
HCl
F2
CO2
C3 H8
O3
SO2
Cl2
2.016)16.0417.03
26.04
27.03
28.01
28.02
28.9
32.00 1.4370.90 3.17
2.86
2.14
1.97
1.96
1.70
1.63
1.5234.09
36.46
38.00
44.01
44.09
48.00
64.071.25
1.25
1.21
1.16
0.760
0.716
0.900
1.29O2
1
PV
Ideal Gas Equation
TV
For one mole of a gas at STP, R constant:
(1 atm)(22.4L)
273K=R = 0.082
L-atm
mol-K
nV nT
P=V R
nT
PV
=R TP V m
M
= n R TP V
=R T
MmPV
=PM
dRT
Equation of State
Ideal Gas Equation
[pressure][Volume]
[temperature][mol]=[R] =
[force][volume]
[area][temperature][mol]
=[force][length]
[temperature][mol]=
[energy]
[temperature][mol]
R = 8.134 J mol-1 K-1 ~ 2 Cal mol -1 K-1
The ideal gas constant has energy/mol degrees dimensions
[R]
Gas Stoichiometry
Cu(s) + 4H+ + 2NO3- (aq) Cu+2 (aq) + 2NO2 (aq) + 2H2O
Concentrated nitric acid acts on copper and produces nitrogen dioxide and dissolved copper. 6.80 g Cu is consumed and NO2 is collected at a pressure of .970atm and a temperature of 45°C (318 K) . Calculate the volume of NO2 produced.
63.55 g Cu
1 mol Cux6.80 g Cu x
1 mol Cu
2 mol NO2 = 0.214 mol NO2
n R T
P=V = 5.76 L NO2
http://www.sp.uconn.edu/~terry/229sp98/Ncycleanim.html
Real Gases
Follow the ideal gas law at sufficiently low densities
Gas molecules attract one another
Both factors increase in importance when the molecules are close together (high P. low T).
Gas molecules occupy a finite volume
n R T
P V=z
Deviations from ideality are quantified by the Compressibility factor z
Real Gases Intermolecular Forces
0
0.5
1.0
1.5
Com
pres
ibil
ity
rati
o
2.0
0
P (atm)200 400 600 800
Ideal Gas
H2
CH4
N2
0
0.5
1.0
1.5
Com
pres
ibil
ity
rati
o2.0
0
P (atm)200 400 600 800
Ideal Gas
600 °C
-100 °C
25 °C
Nitrogen at several T
Van der Waals Equation
P +an2
V2
⎛
⎝ ⎜ ⎜
⎞
⎠ ⎟ ⎟ V −nb( ) =nRT
b = constant representing volume excluded per mole of molecules
a = depends on the strength of attractive forces
n2
V2Proportional to reduction of wall collisions due to cluster formation.
Air Pollution
O2
2O
O2 O+ O3
O2O+O3
+ heat
CCl3F
CCl2F + Cl .
Cl . + O3 ClO . + O2
ClO . + O O2 + Cl .
Allotropic Transformation
Ozone shield
Ozone destruction